GENERAL REFERENCES: Foust, Wenzel, Clump, Maus, and Anderson, Princi- “Drop Phenomena Affecting Liquid Extraction,” in Drew

on,” in Drew et al. (eds.), Advances

ples of Unit Operations, 2d ed., Wiley, New York, 1980. Schweitzer (ed.), Hand- in Chemical Engineering, vol. 4, Academic, New York, 1963. Molyneux, Chem-
book of Separation Techniques for Chemical Engineers, 2d ed., McGraw-Hill, ical Plant Design, vol. I, Butterworth, Washington, 1965. Olney and Miller,
New York, 1988. Sorenson and Arlt, “Liquid-Liquid Equilibrium Data Collec- “Liquid Extraction,” in Acrivos (ed.) Modern Chemical Engineering, vol 1, Rein-
tion,” DECHEMA, Frankfurt, Germany, Binary Systems vol V, part 1, 1979, hold, New York, 1963. Olson and Stout, “Mixing and Chemical Reactions,” in
Ternary Systems vol V, part 2, 1980, Ternary & Quaternary Systems, vol 5, part Uhl and Gray (eds.), Mixing, vol. 2, Academic, New York, 1967. Reitma, “Seg-
3, 1980, Macedo and Rasmussen, Supplement 1, vol V, part 4, 1987. Treybal, regation in Liquid-Liquid Dispersions,” in Drew et al. (eds.), Advances in
Liquid Extraction, 2d ed., McGraw-Hill, New York, 1963. Treybal, Mass- Chemical Engineering, vol. 5, Academic, New York, 1964. Rod, Misek, and Ster-
Transfer Operations, 3d ed., McGraw-Hill, New York, 1980. Wisniak and Tamir, bacek, Liquid Extraction, Statne Nakladatelstor Techniki Literatury, Prague,
Liquid-Liquid Equilibrium and Extraction: A Literature Source Book, part A, 1964. Sideman, “Direct-Contact Heat Transfer between Immiscible Liquids,”
Elsevier, Amsterdam, 1981. Lo, Baird, and Hanson, Handbook of Solvent in Drew et al. (eds.), Advances in Chemical Engineering, vol. 6, Academic, New
Extraction, Wiley, New York, 1983. Astarita, Mass Transfer with Chemical Reac- York, 1966. Treybal, Mechanically Aided Liquid Extraction, ibid., vol. 1, 1956.
tions, Elsevier, New York, 1967. Calderbank, “Mass Transfer,” in Uhl and Gray Ziolkowski, Liquid Extraction in the Chemical Industry, Gos. Nauchn. Tekln.
(eds.), Mixing, vol. 2, Academic, New York, 1967. Cremer and Davies, Chemical Izd. Khim. Lit, Leningrad, 1963. Cusack, Fremeaux, and Glatz, “A Fresh Look
Engineering Practice, vol. 5, Academic, New York, 1958. Davies, “Mass Transfer at Liquid-Liquid Extraction,” part 1, Extraction Systems, Chemical Engineer-
and Interfacial Phenomena,” in Drew, Hoopes, and Vermeulen (eds.), Advances ing, vol. 98, no. 2, p. 66–67, Feb. 1991. Cusack, and Fremeaux, part 2, “Inside
in Chemical Engineering, vol. 4, Academic, New York, 1963. Hanson (ed.), the Extractor,” Chemical Engineering, vol. 98, no. 3, p. 132–138, Mar. 1991.
Recent Advances in Liquid-Liquid Extraction, Pergamon, New York, 1971. Cusack and Karr, part 3, “Extractor Design and Specification,” Chemical Engi-
Hyman, Mixing and Agitation, ibid, vol. 3, 1962. Kalichevsky and Kobe, Petro- neering, vol. 98, no. 4, p. 112–120, Apr. 1991.
leum Refining with Chemicals, Van Nostrand, Princeton, N.J., 1965. Kintner,

LIQUID-LIQUID EXTRACTION OPERATIONS

Liquid-liquid extraction is a process for separating components in sensitive, like antibiotics, or relatively nonvolatile, like mineral salts,
solution by their distribution between two immiscible liquid phases. and liquid-liquid extraction may provide the most cost-effective sepa-
Such a process can also be simply referred to as liquid extraction or ration process. However, the potential use of distillation should
solvent extraction; however, the latter term may be confusing generally be evaluated carefully before considering liquid-liquid ex-
because it also applies to the leaching of a soluble substance from a traction. An extraction process usually requires (1) liquid-liquid
solid. extraction, (2) solvent recovery, and (3) raffinate desolventizing.
Since liquid-liquid extraction involves the transfer of mass from one Several examples of cost-effective liquid-liquid extraction processes
liquid phase into a second immiscible liquid phase, the process can be include the recovery of acetic acid from water (Fig. 15-1), using ethyl
carried out in many different ways. The simplest example involves the ether or ethyl acetate as described by Brown [Chem. Eng. Prog.,
transfer of one component from a binary mixture into a second immis- 59(10), 65 (1963)], or the recovery of phenolics from water as
cible liquid phase. One example is liquid-liquid extraction of an impu- described by Lauer, Littlewood, and Butler [Iron Steel Eng., 46(5), 99
rity from wastewater into an organic solvent. This is analogous to (1969)] with butyl acetate, or with isopropyl ether as described by
stripping or absorption in which mass is transferred from one phase to Wurm [Glückauf, 12, 517 (1968)], or with methyl isobutyl ketone as
another. Transfer of the dissolved component (solute) may be described by Scheibel [“Liquid-Liquid Extraction,” in Perry & Weiss-
enhanced by the addition of “salting out” agents to the feed mixture or
by adding “complexing” agents to the extraction solvent. Or in some
cases a chemical reaction can be used to enhance the transfer, an
example being the use of an aqueous caustic solution to remove phe-
nolics from a hydrocarbon stream. A more sophisticated concept of
liquid-liquid fractionation can be used in a process to separate two
solutes completely. A primary extraction solvent is used to extract one
of the solutes from a mixture (similar to stripping in distillation), and a
wash solvent is used to scrub the extract free from the second solute
(similar to rectification in distillation).

USES FOR LIQUID-LIQUID EXTRACTION

Liquid-liquid extraction is used primarily when distillation is imprac-
tical or too costly to use. It may be more practical than distillation
when the relative volatility for two components falls between 1.0 and
1.2. Likewise, liquid-liquid extraction may be more economical than
distillation or steam-stripping a dissolved impurity from wastewater
when the relative volatility of the solute to water is less than 4. In one
case discussed by Robbins [Chem. Eng. Prog., 76 (10), 58 (1980)], liq-
uid-liquid extraction was economically more attractive than carbon-
bed or resin-bed adsorption as a pretreatment process for wastewater
detoxification before biotreatment.
In other cases the components to be separated may be heat- FIG. 15-1 Solvent extraction of acetic acid from water.

15-4
 LIQUID-LIQUID EXTRACTION OPERATIONS 15-5

burg (eds.), Separation and Purification, 3d ed., Wiley, New York, raffinate requires practically no desolventizing because the solubility
1978, chap. 3]. The solvent is recovered by distillation, and the raffi- of the solvents in water is extremely low. Most of the solvent loss
nate is desolventized by steam stripping. In some cases the extraction occurs because of the entrainment of small droplets in the water. The
solvent may have a higher boiling point than the solute to achieve economic utility of a liquid-liquid extraction process depends strongly
reduced energy consumption, but a buildup of heavies in the recycle on the solvent selected and on the procedures used for solvent recov-
solvent can create another problem. ery and raffinate desolventizing. After these matters have been con-
The Udex process (Fig. 15-2) is a cost-effective liquid-liquid frac- sidered, the selection and design of an extraction device or assembly
tionation process for the separation of aromatics from aliphatics as can be considered in proper perspective.
described by Grote [Chem. Eng. Prog., 54(8), 43 (1958)]. In this
process the extraction solvent, diethylene or triethylene glycol, is
recovered by steam distillation, and the raffinate and extract streams DEFINITIONS
are desolventized by water extraction. Subsequent process modifica- The feed to a liquid-liquid extraction process is the solution that con-
tions described by Symoniak, Ganju, and Vidueira [Hydrocarbon tains the components to be separated. The major liquid component in
Process., 139 (September 1981)] use tetraethylene glycol as the the feed can be referred to as the feed solvent. Minor components in
extraction solvent and a mixture of light aliphatics and benzene as the solution are often referred to as solutes. The extraction solvent, or
wash solvent to the main extractor. Water condensate from the steam just plain solvent, is the immiscible liquid added to a process for the
distillation is used to extract residual extraction solvent from the raffi- purpose of extracting a solute or solutes from the feed. The extraction-
nate and extract streams, so distillation for drying the extraction sol- solvent phase leaving a liquid-liquid contactor is called the extract.
vent has been eliminated. Solids are removed from recycle extraction The raffinate is the liquid phase left from the feed after being con-
solvent by filtration, while acids and heavies are removed by a solid tacted by the second phase. A wash solvent is a liquid added to a liq-
adsorbent bed. Other processes similar to this use sulfolane (tetra- uid-liquid fractionation process to wash or enrich the purity of a solute
hydrothiophene-1,1-dioxide) or NMP (N-methyl-pyrrolidone) as the in the extract phase.
extraction solvent. A theoretical or equilibrium stage is a device or combination of
Another example of a cost-effective liquid-liquid extraction process devices that accomplishes the effect of intimately mixing two immisci-
is the one used for recovery of uranium from ore leach liquors (Fig. ble liquids until equilibrium concentrations are reached, then physi-
15-3). In this case the solvents, alkyl phosphates in kerosine, are cally separating the two phases into clear layers. Crosscurrent
recovered by liquid-liquid extraction using a strip solution, and the extraction (Fig. 15-4) is a cascade, or series of stages, in which the
raffinate R from one extraction stage is contacted with additional fresh
solvent S in a subsequent stage.
Countercurrent extraction (Fig. 15-5) is an extraction scheme in
which the extraction solvent enters the stage or end of the extraction
farthest from where the feed F enters and the two phases pass coun-
tercurrently to each other. The objective is to transfer one or more
components from the feed solution F into the extract E. When a
staged contactor is used, the two phases are mixed with droplets of
one phase suspended in the other, but the phases are separated before
leaving each stage. When a differential contactor is used, one of the
phases can remain dispersed as droplets throughout the contactor as
the phases pass countercurrently to each other. The dispersed phase is
then allowed to coalesce at the end of the device before being dis-
charged.
Liquid-liquid fractionation, or fractional extraction (Fig. 15-6),
is a sophisticated scheme for nearly complete separation of one solute
from a second solute by liquid-liquid extraction. Two immiscible liq-
uids travel countercurrently through a contactor, with the solutes
being fed near the center of the contactor. The ratio of immiscible-
FIG. 15-2 Udex process.
liquid flow rates is operated so that one of the phases preferentially
moves the first solute to one end of the contactor and the other phase
moves the second solute to the opposite end of the contactor. Another
way to describe the operation is that a primary solvent S preferentially
extracts, or strips, the first solute from the feed F and a wash solvent

FIG. 15-3 Liquid-liquid extraction of uranium. FIG. 15-4 Crosscurrent extraction. FIG. 15-5 Countercurrent extraction.
15-6 LIQUID-LIQUID EXTRACTION OPERATIONS AND EQUIPMENT

W scrubs the extract free from the unwanted second solute. The sec-
ond solute leaves the contactor in the raffinate stream.
Dissociation extraction is the process of using chemical reaction
to force a solute to transfer from one liquid phase to another. One
example is the use of a sodium hydroxide solution to extract phenolics,
acids, or mercaptans from a hydrocarbon stream. The opposite trans-
fer can be forced by adding an acid to a sodium phenate stream to
spring the phenolic back to a free phenol that can be extracted into
an organic solvent. Similarly, primary, secondary, and tertiary amines
can be protonated with a strong acid to transfer the amine into a water
solution, for example, as an amine hydrochloride salt. Conversely, a
strong base can be added to convert the amine salt back to free base,
which can be extracted into a solvent. This procedure is quite com-
mon in pharmaceutical production.
Fractionation dissociation extraction involves both the chemi-
cal reaction and the fractionation scheme for the separation of com-
ponents by their difference in dissociation constants as described by
Colby [in Hanson (ed.), Recent Advances in Liquid-Liquid Extrac-
FIG. 15-6 Liquid-liquid fractionation. tion, Pergamon, New York, 1971, chap. 4].

PHASE EQUILIBRIA

The separation of components by liquid-liquid extraction depends pri- For low concentrations in which the equilibrium line is linear the
marily on the thermodynamic equilibrium partition of those compo- value of K′ is equal to m.
nents between the two liquid phases. Knowledge of these partition The value of K′ is one of the main parameters used to establish the
relationships is essential for selecting the ratio of extraction solvent to minimum ratio of extraction solvent to feed solvent that can be
feed that enters an extraction process and for evaluating the mass- employed in an extraction process. For example, if the partition ratio
transfer rates or theoretical stage efficiencies achieved in process K′ is 4, then a countercurrent extractor would require 0.25 kg or more
equipment. Since two liquid phases that are immiscible are used, the of extraction-solvent flow to remove all the solute from 1 kg of feed-
thermodynamic equilibrium involves considerable evaluation of non- solvent flow.
ideal solutions. In the simplest case a feed solvent F contains a solute The relative separation, or selectivity, α between two compo-
that is to be transferred into an extraction solvent S. nents, b and c, can be described by the ratio of the two partition ratios
[Eq. (15-5)].
EQUILIBRIUM PARTITION RATIOS α(b/c) = K°b /K°c = K b /K c = K′b /K′c (15-5)
The weight fraction of solute in the extract phase y divided by the This is analogous to relative volatility in distillation.
weight fraction of solute in the raffinate phase x at equilibrium is
called the partition ratio, K [Eq. (15-1)].
PHASE DIAGRAMS
K = y/x (15-1)
Ternary-phase equilibrium data can be tabulated as in Table 15-1
Thermodynamically the partition ratio K° is derived in mole fractions
and then worked into an electronic spreadsheet as in Table 15-2 to be
y° and x° [Eq. (15-2)].
presented as a right-triangular diagram as shown in Fig. 15-7. The
K° = y°/x° (15-2) weight-fraction solute is on the horizontal axis and the weight-fraction
extraction-solvent is on the vertical axis. The tie-lines connect the points
For shortcut calculations the partition ratio K′ in Bancroft [Phys. Rev.,
that are in equilibrium. For low-solute concentrations the horizontal
3, 120 (1895)] coordinates using the weight ratio of solute to extrac-
scale can be expanded. The water-acetic acid-methylisobutylketone
tion solvent in the extract phase Y and the weight ratio of solute to
ternary is a Type I system where only one of the binary pairs, water-
feed solvent in the raffinate phase X is preferred [Eq. (15-3)].
MIBK, is immiscible. In a Type II system two of the binary pairs are
K′ = Y/X (15-3) immiscible, i.e. the solute is not totally miscible in one of the liquids.
Many immiscible-liquid systems exhibit a critical solution tem-
In shortcut calculations the slope of the equilibrium line in Bancroft
perature beyond which the system no longer separates into two liq-
(weight-ratio) coordinates m is also used [Eq. (15-4)].
uid phases. This is shown in Fig. 15-8, in which an increase in
m = dY/dX (15-4) temperature can change a Type II system to a Type I system above the

TABLE 15-1 Water–Acetic Acid–Methyl Isobutyl Ketone, 25°C*

Weight % in raffinate Weight % in extract
Water Acetic acid MIBK X Water Acetic acid MIBK Y
98.45 0 1.55 0 2.12 0 97.88 0
95.46 2.85 1.7 0.0299 2.80 1.87 95.33 0.0196
85.8 11.7 2.5 0.1364 5.4 8.9 85.7 0.1039
75.7 20.5 3.8 0.2708 9.2 17.3 73.5 0.2354
67.8 26.2 6.0 0.3864 14.5 24.6 60.9 0.4039
55.0 32.8 12.2 0.5964 22.0 30.8 47.2 0.6525
42.9 34.6 22.5 0.8065 31.0 33.6 35.4 0.9492
*From Sherwood, Evans, and Longcor [Ind. Eng. Chem., 31, 599 (1939)].